Casanova David, Cirera Jordi, Llunell Miquel, Alemany Pere, Avnir David, Alvarez Santiago
Departament de Química Inorgànica and Centre de Recerca en Química Teòrica, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain.
J Am Chem Soc. 2004 Feb 18;126(6):1755-63. doi: 10.1021/ja036479n.
A definition of minimum distortion paths between two polyhedra in terms of continuous shape measures (CShM) is presented. A general analytical expression deduced for such pathways makes use of one parameter, the minimum distortion constant, that can be easily obtained through the CShM methodology and is herein tabulated for pairs of polyhedra having four to eight vertexes. The work presented here also allows us to obtain representative model molecular structures along the interconversion pathways. Several commonly used polytopal rearrangement pathways are shown to be in fact minimum distortion pathways: the spread path leading from the tetrahedron to the square, the Berry pseudorotation that interconverts a square pyramid and a trigonal bipyramid, and the Bailar twist for the interconversion of the octahedron and the trigonal prism. Examples of applications to the analysis of the stereochemistries of several families of metal complexes are presented.
本文提出了一种基于连续形状度量（CShM）的两个多面体之间最小畸变路径的定义。推导得到的此类路径的一般解析表达式使用了一个参数，即最小畸变常数，该参数可通过CShM方法轻松获得，本文还列出了具有四至八个顶点的多面体对的该常数。本文所做的工作还使我们能够沿着相互转化路径获得具有代表性的模型分子结构。结果表明，几种常用的多面体重排路径实际上就是最小畸变路径：从四面体到正方形的扩展路径、使正方锥和三角双锥相互转化的Berry假旋转以及使八面体和三角棱柱相互转化的Bailar扭转。文中给出了将其应用于分析几类金属配合物立体化学的实例。
